JPH06191905A - Sound insulating laminated glass intermediate film and sound insulating laminated glass using the same - Google Patents

Abstract

PURPOSE:To provide an interliner for a laminated glass having various excellent properties (transparency, weather resistance, adhesivity and scattering-prevention of fractured glass pieces) of an interliner composed of a plasticized polyvinyl acetal resin and exhibiting excellent sound-insulating performance over a wide temperature range (e.g. -10 to + or -80 deg.C) and to provide a laminated glass containing the interliner. CONSTITUTION:This sound-insulating interliner is composed of a plasticizer and a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol with a 4-10C aldehyde. The amount of resin having an acetalization degree higher than the average acetalization degree by >=10mol% and that of resin having an acetalization degree lower than the average acetalization degree by >=10% account for 10-30% of the total resin, respectively. The sound-insulating interliner is sandwiched and bonded between a pair of glass plates to obtain a sound-insulating laminated glass.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sound insulating laminated glass intermediate film and a sound insulating laminated glass using the same.

[0002]

2. Description of the Related Art Laminated glass in which an interlayer film composed of a polyvinyl acetal resin and a plasticizer is adhered between two transparent glass plates is widely used for window glass for automobiles, aircrafts, buildings and the like.

As the polyvinyl acetal resin, a resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde and other aldehydes having 4 to 10 carbon atoms is used (for example, JP-A-56-82806).
JP-A-62-27814).

[0004]

This type of laminated glass has various excellent properties such as good weather resistance, good adhesiveness, no scattering of glass fragments, good transparency, and no optical distortion. However, the sound insulation is inferior. Especially 2000H
In the mid-high range near z, the sound insulation is lowered by the so-called coincidence effect.

The present invention is intended to solve the above problems, and its object is to make full use of various excellent properties of a laminated glass using an interlayer film composed of a conventional polyvinyl acetal resin and a plasticizer. Another object of the present invention is to provide an interlayer film for a sound-insulating laminated glass and a sound-insulating laminated glass that exhibit excellent sound insulating properties in a wide temperature range.

[0006]

In order to achieve the above object, the interlayer film for a sound insulating laminated glass of the present invention is a plastic with a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 10 carbon atoms. The distribution of the degree of acetalization of the polyvinyl acetal resin is an average degree of acetalization (mol%) + 10 mol%
It is configured to occupy 10 to 30% above and occupy 10 to 30% below the average degree of acetalization (mol%)-10 mol%.

The sound-insulating laminated glass of the present invention is
The above-mentioned interlayer film for sound-insulating laminated glass is adhered between two glass plates.

The polyvinyl acetal resin used in the present invention is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 10 carbon atoms. In the preparation of this polyvinyl acetal resin, the polyvinyl alcohol preferably has an average degree of polymerization of 1000 to 3000. If the average degree of polymerization is less than 1000, the penetration resistance of the laminated glass is reduced. On the contrary, if the average degree of polymerization exceeds 3000, it becomes difficult to form the film.

The average degree of saponification of polyvinyl alcohol is preferably 78 mol% or more. When the average degree of saponification is less than 78 mol%, the transparency and heat resistance of the film are lowered, and the reactivity with aldehyde is also lowered.

As the aldehyde used for acetalization, an aldehyde having 4 to 10 carbon atoms is used. For example, n-butyraldehyde, isobutyraldehyde, 2
-Ethyl butyraldehyde, n-heptyl aldehyde,
n-octyl aldehyde, n-nonyl aldehyde, n-
Aliphatic and aromatic aldehydes such as decylaldehyde, benzaldehyde, cinnamaldehyde and the like can be mentioned. These aldehydes may be used alone or in combination of two or more.

If the aldehyde has less than 4 carbon atoms, sufficient sound insulation cannot be obtained. On the other hand, when the aldehyde has more than 10 carbon atoms, the reactivity of acetalization is remarkably reduced, and the polyvinyl acetal resin obtained has low rigidity and sound insulation.

In the polyvinyl acetal resin used in the present invention, the acetalization degree distribution of the resin occupies 10 to 30% of the average acetalization degree (mol%) + 10 mol% or more and the average acetalization degree (mol%)- It is necessary to prepare 10 mol% or less to occupy 10 to 30%.

When the acetalization degree distribution of the resin is one of the average acetalization degree (mol%) + 10 mol% or more and -10 mol% or less, or less than 10%, it may be at a low or high environmental temperature. Sufficient sound insulation cannot be obtained. On the contrary, when the acetalization degree distribution of the resin is more than 30% in the average acetalization degree (mol%) +10 mol% or more and -10 mol% or less, or more than 30%, the sound insulation property at low temperature or high temperature is obtained. However, sufficient sound insulation cannot be obtained at ambient temperatures near room temperature.

The polyvinyl acetal resin is generally prepared by dissolving polyvinyl alcohol in hot water, keeping the obtained aqueous solution at a predetermined temperature, adding the required acid catalyst and aldehyde thereto, and stirring the mixture. While the acetalization reaction proceeds, the reaction temperature is then raised to maintain a constant temperature for aging to complete the reaction, followed by neutralization, washing with water and drying.

When a polyvinyl acetal resin is prepared under ordinary reaction conditions, a large amount of aldehyde and acid catalysts that react with polyvinyl alcohol are present under high temperature conditions.
The acetalization reaction is very fast. Therefore, the acetalization reaction rapidly progresses on the surface of the resin particles, and conversely, the reaction hardly progresses at the central portion of the particles.

Therefore, in the obtained polyvinyl acetal resin, the acetalization degree distribution of the polyvinyl acetal resin occupies about 0 to 7% in the average acetalization degree (mol%) + 10 mol% or more and the average acetalization degree (mol %) -10 mol% or less occupies about 0 to 7%, and when such a polyvinyl acetal resin is used,
Sufficient sound insulation cannot be obtained.

In the present invention, special reaction conditions are adopted to prepare the target polyvinyl acetal resin. For example, the acetalization degree distribution of the resin is greatly influenced by the temperature when the acid catalyst and the aldehyde are added to the polyvinyl alcohol aqueous solution, and by making this temperature relatively high, the resin having the target acetalization degree distribution is obtained. Can be obtained. The appropriate temperature varies depending on the degree of polymerization or saponification of polyvinyl alcohol used and the type of aldehyde, but is generally preferably 20 ° C. or higher.

The distribution of the degree of acetalization of the resin is influenced by the method of adding the aldehyde. For the resin having the target degree of acetalization, for example, polyvinyl alcohol is dissolved in hot water to obtain an aqueous solution. The temperature is maintained at a predetermined temperature, an acid catalyst and 40% or less of the total addition amount of aldehyde are added, and the acetalization reaction proceeds while stirring. Then, the reaction solution is kept at a required constant temperature, the remaining aldehyde is slowly added little by little, and then the reaction solution is matured at a constant temperature to complete the reaction.

In the above method, the rate of adding the remaining aldehyde varies depending on the temperature maintained at the constant temperature and the amount of the remaining aldehyde, but the higher the temperature of the constant temperature and the higher the amount of the remaining aldehyde, the slower the remaining aldehyde. Need to be added. Generally, 30 minutes to 3 hours is preferable.

Further, the resin having a target degree of acetalization distribution has a method of increasing the amount of the acid catalyst and a very high temperature rising rate when the temperature is increased to a constant temperature after adding the aldehyde and the acid catalyst. It can also be obtained by the method. However, it is not easy to control the degree of acetalization of the polyvinyl acetal resin obtained by these methods.

Further, the resin having a target degree of acetalization degree distribution is prepared by preparing two or more kinds of polyvinyl acetal resins having different average acetalization degrees, and mixing and mixing these resins at various mixing ratios. You can also

In the present invention, the average acetalization degree of the polyvinyl acetal resin is generally 40 to 75 mol%.
Is preferred. When the average degree of acetalization of the resin is less than 40 mol%, the compatibility with the plasticizer becomes poor, and it becomes difficult to mix the amount of the plasticizer required for ensuring sound insulation and penetration resistance. On the contrary, it takes a long reaction time to obtain a resin having an average acetalization degree exceeding 75 mol%, which is not preferable in the process.

The distribution of the degree of acetalization of the resin can be measured by liquid chromatography, thin layer chromatography or the like. For example, in the case of measurement by liquid chromatography, first, a polar liquid (for example, water) is allowed to flow through a column as an eluent, and a polyvinyl acetal resin is completely dissolved in a solvent such as ethanol and injected into the column. Only the resin part with high temperature (part with low degree of acetalization) is detected as outflow.

After that, by gradually decreasing the polarity of the eluent (for example, water → ethanol → ethyl acetate →), resin portions with lower polarity (higher acetalization degree portions) are sequentially detected by outflow. Then, by finally flowing a non-polar liquid (for example, toluene), all outflow is detected even to the resin portion having a low polarity (high acetalization degree portion). The acetalization degree distribution is obtained from these values.

The polyvinyl acetal resin thus prepared is mixed with a predetermined amount of a plasticizer and the mixture is extruded.
A film is formed into a sheet by the calendar method, the pressing method, etc.,
An interlayer film for laminated glass is manufactured.

The film thickness of the resin film is similar to that of a normal interlayer film for laminated glass, and is generally 0.3 to 1.6.
The range is mm. If the film thickness is less than 0.3 mm, it is not sufficient to exhibit good sound insulation performance and weather resistance. The thicker the film, the better the sound insulation, but practically it is 1.6 mm or less.

As the plasticizer, known plasticizers used in this type of interlayer film, for example, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexoate, triethylene. Glycol dicaprylate, triethylene glycol di-n-heptate, tetraethylene glycol di-n-heptate and the like are preferably used.

Such a plasticizer is generally 20 to 60 parts by weight, preferably 30 to 55 parts by weight, based on 100 parts by weight of the resin.
Parts by weight are mixed. If the content of the plasticizer is less than 20 parts by weight, the penetration resistance of the laminated glass decreases. vice versa,
When the content of the plasticizer exceeds 60 parts by weight, the plasticizer oozes out, which adversely affects the adhesiveness of the laminated glass.

The polyvinyl acetal resin contains known additives used in the interlayer film for laminated glass, such as an ultraviolet absorber, a light stabilizer, an antioxidant, an adhesion modifier, a surfactant and a coloring agent. It can be blended.

As the ultraviolet absorber, a benzotriazole type one, for example, Tinuvin P manufactured by Ciba-Geigy Co.,
Examples include Tinuvin 320, Tinuvin 326, Tinuvin 328 and the like. Examples of the light stabilizer include hindered amine-based light stabilizers such as ADEKA STAB LA-57 manufactured by Asahi Denka Co., Ltd.

Examples of the antioxidant include phenol-based antioxidants such as Sumilizer BHT manufactured by Sumitomo Chemical Co., Ltd. and Irganox 1010 manufactured by Ciba Geigy.

Examples of the adhesion modifier include metal salts of carboxylic acids, for example, potassium salts and sodium salts of octylic acid, hexylic acid, butyric acid, acetic acid, formic acid and the like. Also,
Examples of the surfactant include sodium lauryl sulfate and alkylbenzene sulfonic acid.

As the film-forming method, a commonly used extrusion molding method is preferred, but not particularly limited. The intermediate film thus obtained may be laminated with a film having other functions, for example, a polyester film having a heat ray reflecting function having a layer coated with fine particles of silver or the like. Further, a usual plasticized polyvinyl butyral interlayer film, which is often used as an interlayer film for general laminated glass, may be laminated and used. When laminating a conventional plasticized polyvinyl butyral interlayer, a multilayer extrusion molding method is suitable.

In order to manufacture a laminated glass using the sound insulating laminated glass interlayer film of the present invention, the above interlayer film is sandwiched between two inorganic glass plates or a highly rigid organic glass plate such as polycarbonate. Is put in a rubber bag, for example, and pre-bonded at about 70 to 110 ° C under vacuum suction, and then at about 120 to 150 ° C in an autoclave.
Then, the main adhesion is performed at a pressure of about 10 to 15 kg / cm ² . Thus, the sound insulating laminated glass of the present invention is manufactured.

[0035]

According to the inventor's knowledge, the sound insulation of a laminated glass using an interlayer film composed of a polyvinyl acetal resin and a plasticizer is related to the ambient temperature and has a maximum value at a certain temperature. The maximum value shifts to the high temperature side as the degree of acetalization of the resin is low, and shifts to the low temperature side as the degree of acetalization of the resin is high. Also, the wider the acetalization degree distribution of the resin, the wider the temperature range showing sound insulation, but the lower the level of sound insulation.
The narrower the acetalization degree distribution, the narrower the temperature range in which the sound insulation property is, but the higher the sound insulation level.

The polyvinyl acetal resin used in the present invention is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 10 carbon atoms, and the acetalization degree distribution of the resin has an average acetalization degree (mol%) +
10 to 30% occupy 10 mol% or more and 10 to 30% occupy less than the average degree of acetalization (mol%)-10 mol%.

When a polyvinyl acetal resin having such a specific degree of acetalization distribution is used, it is particularly preferable that
Sound insulation is prevented from decreasing due to coincidence effect in the mid-high range near 000 Hz, and sound insulation in a wide temperature range from low temperature to high temperature (for example, -10 to 80 ° C) compared to that using conventional polyvinyl acetal resin. The level of can be kept high. Further, by appropriately setting the average acetalization degree, it is possible to move the temperature range in which the sound insulation level is high to the low temperature side or the high temperature side.

[0038]

EXAMPLES Examples and comparative examples of the present invention will be shown below. Example 1 Preparation of Polyvinyl Acetal Resin 193 g of polyvinyl alcohol having a polymerization degree of 1700 and a saponification degree of 98.9 mol% was added to 2900 g of pure water and dissolved by heating. The temperature of this solution was adjusted to 29 ° C., 201 g of hydrochloric acid having a concentration of 35% and 192 g of n-octyl aldehyde were added, the liquid temperature was lowered to 20 ° C. and this temperature was maintained to precipitate the reaction product.

Then, the liquid temperature was maintained at 35 ° C. for 5 hours to complete the reaction, and the mixture was neutralized, washed with water and dried to obtain a white powdery polyvinyl acetal resin. The average degree of acetalization of this resin was 63.6 mol%, and the distribution of degree of acetalization was 28 at an average degree of acetalization (mol%)-10 mol% or less.
%, And 17% of the average acetalization degree (mol%) + 10 mol% or more.

Production of interlayer film for laminated glass 100 parts by weight of the above resin and 40 parts by weight of triethylene glycol-di-2-ethylbutyrate as a plasticizer were mixed, and this was sufficiently melted and kneaded with a mixing roll and kneaded. The product was press-molded with a press molding machine at 150 ° C. for 30 minutes to obtain a laminated glass interlayer film having a thickness of 0.76 mm.

Production of Laminated Glass The above-mentioned interlayer film for laminated glass is sandwiched from both sides by transparent float glass (length 30 cm × width 30 cm × thickness 3 mm), and the sandwich body is put in a rubber bag for 20 t.
After degassing at a vacuum degree of orr for 20 minutes, the degassed state was transferred to an oven at 90 ° C., and vacuum pressing was performed while holding at 90 ° C. for 30 minutes.

The laminated glass pre-bonded in this manner was heated at a temperature of 135 ° C. and a pressure of 1 by an air type autoclave.
Main bonding was carried out for 20 minutes under the condition of 2 kg / cm ² to produce a laminated glass.

Measurement of sound insulation of laminated glass This laminated glass was used as a vibration generator (G
21-005D: manufactured by Shinken Co., Ltd., and the vibration characteristics obtained by the vibration are measured by a mechanical impedance amplifier (XG-8).
1: Amplified by Rion Co., and the vibration spectrum is FFT analyzer (FFT spectrum analyzer (HP
3582A: manufactured by Yokogawa Hewlett-Packard Co.).

The transmission loss (dB) was calculated from the loss coefficient thus obtained and the resonance frequency ratio with the glass (measurement temperature -10 to 80 ° C.), and the frequency (Hz) and the transmission loss (dB) were calculated. A graph showing the relationship between
The minimum transmission loss (TL value) near 0 Hz was obtained. The results are summarized in Table 1.

Example 2 In the production of the polyvinyl acetal resin of Example 1,
192 g of n-octyl aldehyde was changed to 192 g of n-hexyl aldehyde, and the temperature of the polyvinyl alcohol aqueous solution to which n-hexyl aldehyde was added was changed from 29 ° C. to 32 ° C.
Changed to. Other than that was performed like Example 1.

In this case, the polyvinyl acetal resin has an average acetalization degree of 62.9 mol%, the acetalization degree distribution occupies 19% below the average acetalization degree (mol%)-10 mol%, and the average acetalization degree is Degree (mol%) +
It occupied 12% to 10 mol% or more. The results are summarized in Table 1.

Example 3 In the production of the polyvinyl acetal resin of Example 1,
193 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 98.9 mol%, a degree of polymerization of 1700 and a degree of saponification of 87.8
Changed to 193 g of mol% polyvinyl alcohol. In addition, 192 g of n-octyl aldehyde was changed to 192 g of n-butyraldehyde, and the temperature of the polyvinyl alcohol aqueous solution to which n-butyraldehyde was added was changed from 29 ° C to 40 ° C.
Changed to. Further, the plasticizer 40 parts by weight was changed to 50 parts by weight. Other than that was performed like Example 1.

In this case, the polyvinyl acetal resin has an average degree of acetalization of 56.9 mol%, the acetalization degree distribution occupies 20% of the average acetalization degree (mol%)-10 mol% or less, and the average acetalization degree. Degree (mol%) +
It occupied 10% to 10 mol% or more. The results are summarized in Table 1.

Example 4 193 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 98.9 mol% was added to 2900 g of pure water and dissolved by heating. The temperature of this solution was adjusted to 15 ° C., 201 g of hydrochloric acid having a concentration of 35% and 58 g of n-octyl aldehyde corresponding to 30% of the total amount added were added, and the liquid temperature was lowered to 8 ° C. to maintain this temperature. Then, the reaction product was deposited.

Thereafter, the liquid temperature was maintained at 35 ° C. and the remaining n
-Adding 134 g of octyl aldehyde over 1 hour,
Hold at a temperature of 35 ° C. for 4 hours to complete the reaction, neutralize,
After washing with water and drying, a white powdery polyvinyl acetal resin was obtained. The average degree of acetalization of this resin is 62.1.
In terms of mol%, the acetalization degree distribution was such that the average acetalization degree (mol%)-15% occupied 10% or less, and the average acetalization degree (mol%) + 10 mol% 10% or more occupied. The same procedure as in Example 1 was performed except that this polyvinyl acetal resin was used. The results are summarized in Table 1.

Example 5 By the conventional method, the average degree of acetalization is 62.4 mol%,
Polyvinyl octyl acetal resin A having an acetalization degree distribution of 56.4 to 68.4 mol%, an average acetalization degree of 52.0 mol%, and an acetalization degree distribution of 45.0 to 59.
A polyvinyl octyl acetal resin B of 0 mol% was prepared, and the resin A and the resin B were mixed at a weight ratio of A: B = 60: 40 to obtain a polyvinyl acetal resin. Other than that was performed like Example 1.

In this case, the polyvinyl acetal resin has an average degree of acetalization of 58.1 mol%, the acetalization degree distribution occupies 15% below the average degree of acetalization (mol%)-10 mol%, and the average acetalization is Degree (mol%) +
It occupied 10% to 10 mol% or more. The results are summarized in Table 1.

Example 6 The thickness of the interlayer film for laminated glass obtained in Example 1 was 0.7.
An intermediate film was used in which 6 mm was 0.38 mm and ordinary polyvinyl butyral intermediate films having a thickness of 0.38 mm were laminated on both sides. Other than that was performed like Example 1. The results are summarized in Table 1.

Comparative Example 1 193 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 98.9 mol% was added to 2900 g of pure water and dissolved by heating. The temperature of this solution was adjusted to 18 ° C., 192 g of n-octylaldehyde and 201 g of hydrochloric acid having a concentration of 35% were added, and the liquid temperature was lowered to 10 ° C. to maintain this temperature to precipitate the reaction product.

Then, the liquid temperature was maintained at 35 ° C. for 5 hours to complete the reaction, and the mixture was neutralized, washed with water, and dried to obtain a white powdery polyvinyl acetal resin. The average acetalization degree of this resin is 64.8 mol%, and the acetalization degree distribution is 8% when the average acetalization degree (mol%) is 10 mol% or less.
It was occupied, and occupied 1% in the average degree of acetalization (mol%) + 10 mol% or more. The same procedure as in Example 1 was performed except that this polyvinyl acetal resin was used. The results are summarized in Table 1.

Comparative Example 2 193 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 98.9 mol% was added to 2900 g of pure water and dissolved by heating. The temperature of this solution was adjusted to 18 ° C., 192 g of n-octylaldehyde and 201 g of hydrochloric acid having a concentration of 35% were added, the liquid temperature was lowered to 13 ° C., and this temperature was maintained to precipitate the reaction product.

Then, the liquid temperature was maintained at 45 ° C. for 3 hours to complete the reaction, and the mixture was neutralized, washed with water and dried to obtain a white powdery polyvinyl acetal resin. This resin has an average degree of acetalization of 65.1 mol% and an acetalization degree distribution of 4% below the average degree of acetalization (mol%)-10 mol%.
Occupancy, and the average acetalization degree (mol%) + 10 mol% or more was not occupied at all. The same procedure as in Example 1 was performed except that this polyvinyl acetal resin was used.
The results are summarized in Table 1.

[0058]

[Table 1]

[0059]

As described above, the interlayer film for sound-insulating laminated glass of the present invention comprises a polyvinyl acetal resin having a specific acetalization degree distribution and a plasticizer, and the sound-insulating laminated glass using this interlayer film is , Prevents deterioration of sound insulation due to the coincidence effect in a wide temperature range, and exhibits excellent sound insulation over a long period of time.

For example, in the case of a combined glass using a conventional interlayer film composed of a polyvinyl acetal resin and a plasticizer, 1
According to the present invention, the sound insulation class 30 specified in JIS A4706 was passed only in the temperature range of 0 to 40 ° C.
Can pass. Moreover, by appropriately setting the average degree of acetalization, it is possible to freely change and set the temperature range in which excellent sound insulation is exhibited, depending on the application.

Further, in the present invention, since the interlayer film for sound-insulating laminated glass is composed of the plasticized polyvinyl acetal resin film as in the conventional case, the penetration resistance against impact is good and the interlayer film for glass and the interlayer film is excellent. It has good adhesiveness, does not scatter glass fragments when broken, is transparent and has excellent safety, and has good weather resistance.

Therefore, the interlayer film and the laminated glass of the laminated glass of the present invention are suitably used for applications requiring sound insulation in a wide temperature range such as skylights of buildings, sunroofs of automobiles and windshields.

Claims (2)

[Claims] 1. A polyvinyl alcohol having 4 to 10 carbon atoms.
Of the polyvinyl acetal resin obtained by acetalizing with the aldehyde of 1. Degree of conversion (mol%)-10 to 10 mol% or less
An interlayer film for a sound-insulating laminated glass, which occupies -30%. 2. A sound-insulating laminated glass, characterized in that the interlayer film for sound-insulating laminated glass according to claim 1 is bonded between two glass plates.